Cuprous complexes



United States Patent O $342,695 CUPROUS CDNPLEXES Christian F. Horn, South Charleston, W. Va, assignor to guilt}?! Carbide Corporation, a corporation of New or No Drawing. Filed Dec. 27, 1950, Ser. No. 78,298 4 Claims. (Cl. 260-438) This invention relates to novel cuprous complexes. More particularly, this invention relates to novel cyclohexanone oxime cuprous complexes useful in aiding the dyeing of acrylonitrile fibers.

It is known in the textile field that synthetic fibers composed of acrylonitrile interpolymers are extremely diflicult to dye. To overcome this difficulty, a copper dyeing method was proposed wherein dyeing occurred in the presence of cuprous ions. Satisfactory dyeing results are obtained using the above described process; however, there are some characteristics of this process which make it less desirable when used in large scale dyeing. When the cuprous ion is produced in the dye bath by the reaction of copper compounds, such as copper sulfate, and reducing agents, several deficiencies arise. These deficiencies center around the reduction of the cupric ion to the active cuprous ion. If the rate of reduction is not carefully controlled, two undseirable occurrences may result. Initially, if the cupric ion is not fully reduced, the chemicals in the bath will be unsatisfactory for use in the dyeing procses. On the other hand, if the cupric ion is over-reduced, metallic copper may be present in the bath which will impair both light stability and the color shade of the fiber. In addition, the above described problems make the dyeing formulations extremely difiicult to reproduce. It is the combination of these problems which have discouraged the use of the cuprous-ion technique. There has therefore been a long felt need in the art for a cuprous-ion complex which could be added directly to the dyebath without going through the reduction process.

I have discovered a class of novel, inorganic acid salts of cuprous complexes of cyclohexanone oxime which can be used to provide outstanding results in the cuprous-ion dyeing technique. A distinct advantage of the compounds of this invention pertains to the fact that not only are the cuprous complexes of cyclohexanone oxime a dyeing aid in acid dyes but also in the dyeing process, the cyclohexanone oxime molecules act as dye carriers. Thus very deep color shades of the dyed fabric can be obtained in the use of the compounds of this invention without the addition of conventional dye carriers.

The cyclohexanone oxime portion of these complexes can be represented by the general formula:

. 3,42,fi95 Patented July 3, 1962 production of the cuprous complexes of this invention include the'cuprous salts such as, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous nitrate, cuprous sulfate, cuprous phosphate, and the like.

The novel cuprous complexes of cyclohexanone oxime Y can be readily produced by reacting the cuprous salts such as, for example cuprous chloride, with a cyclohexanone oxime at a temperature of fromabout 20 C. to about 100 C. for a period of time sufficient for the cuprous complex to form and dissolve in the reactant solution. The reaction can be conducted in in inert organic reaction medium which has a function of a solvent in the event that the cyclohexanone oximestarting material is a solid at room temperature. The time of reaction can range from a few minutes to as long as 24 hours depending on the reaction temperature and the specific reactants used. In general, when the cuprous salts are added to the cyclohexanone oxime to produce the products of this invention, the resulting reaction is exothermic. The temperature is controlled to maintain the preferable temperature of from about 40 C. to about C. After the initial exothermic reaction has run its course, additional heat can be applied to maintain the temperature range and complete the reaction more rapidly.

In producing the novel cuprous complexes of cyclohexanone oxime, the cyclohexanone oxime is preferably employed in mole ratios greater than the equivalent amount of cuprous salt present. The preferred range is from about a 1:1 to 1:4 mole ratio of cuprous salts to cyclohexanone oxime. Higher or lower ratios are operable; however a high excess of cyclohexanone oxime is not economicmly feasible and lower ratios do not make full use of the cuprous salts charged.

In producing the novel cuprous complexes of this invention, it is desirable, although not necessary, to conduct the reaction in an atmosphere of an inert gas free of elemental oxygen, such as an atmosphere of nitrogen, carbon dioxide, helium, and the like. The inert atmosphere aids in decreasing the possible air oxidation of the cuprous salts to the undesirable cupric salts although the cuprous complexes of cyclohexanone oxime can be produced in the presence of air.

Among the cuprous complexes of this invention which can be produced by the above described process are, for example: complex of cuprous chloride and cyclohexanone oxime, complex of cuprous chloride and Z-methylcyclohexanone oxime, complex of cuprous chloride and 3- ethylcyclohexanone oxime, complex of cuprous chloride and 4-isopropylcyclohexanone oxime, complex of cuprous bromide and Z-n-hexylcyclohexanone oxime, complex of cuprous bromide and 2,6-dimethylcyclohexanone oxime, complex of cuprous nitrate and 3,5-diethylcyclohexanone oxime, complex of cuprous nitrate and cyclohexanone oxime, and the like.

The cuprous complexes of the invention can be recovered from their reaction mixtures in high purity by cooling the reaction mixture to precipitate the cuprous complex and isolation by conventional filtration procedures. If the cuprous complex reaction product does not crystallize on cooling, the reaction product can be precipitated by the addition of an organic non-solvent such as acetone, ethyl ether, ethyl acetate, dioxane, and the like. If additional purification of the copper complexes is desired, conventional recrystallization procedures can be used.

The following examples are illustrative:

Example 1 Cuprous chloride (10 grams) was added portionwise with agitation over a period of 5 minutes to 68 grams of thermic.

,cyclohexanone oxime dissolved in 100 milliliters of methanol in a nitrogen atmosphere. The reaction was exo- A voluminous precipitate formed which, after heating the reaction mixture for 4 hours at 60 C., was filtered and dried at room temperature under a nitrogen atmosphere. The recovered precipitate analyzed to be the desired cuprous chloride complex of cyclohexanone oxime Which melted at 120 C.123 C. v The infrared spectrum and analytical data confirmed the' structure as 2C H NOH+CuCL :In an analogous manner, Z-methylcyclohexanone oxime is reacted with cuprous nitrate to obtain the corresponding cuprous nitrate complex of Z-methylcyclohexanone oxime. Additionally, 2,6-dimethy1cyclohexanone oxime is reacted with cuprous sulfate to obtain the correspondoxime.

Example 2 A gram sample of scoured and dried knitted tubing of continuous yarns composed of a terpolymer of acrylonitrile, vinyl chloride and vinylidene chloride [in a ratio, respectively, of 70:20:10] was added to a 200 milliliter total volume aqueous Jdyebath containing 1 percent by weight of the yarn of Pergegal OK (a cationic condensatio'n product pf ethylene oxide and an organic amine marketed by General Aniline and Film Corporation), 2 percent by weight of the yarn of concentrated sulfuric acid, 3 percent by weight of the yarn of Xylene Milling Blue G. L. .(Acid Blue 102-50315) and 2.0 percent by weight of the yarn of the ouprous chloride complex of cyclohexanone oxime. The cuprous chloride complex of cyclohexanone oxime was added as a mixture of 5 parts by weight of acetonitrile to -1 part by weight of cuprous chloride complex of cyclohexanone oxime. The bath temperature was raised to boiling in about 20 minutes and held for 90 minutes at the boiling temperature. The

'dyed fabric was then raised, scoured, rinsed, hydroextracted and dried at 130 C. for 10 minutes. After drying, the dyed fabric had a final K/S value of 13.3. v

The common Fade-Q-Meter test indicated a light fastness rating of the dyed fabric'of 40 hours.

What is claimed is:

l. The cuprous complex produced by the reaction of a cuprous salt of an inorganic mineral acid with ,a cyclohexanone oxime of the formula:

wherein R to R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 6 carbon atoms, at a temperature of from about 20 C. to about C.

2. The cuprous complex produced by'the reaction of euprous chloride with cyclohexanone oxirne at a temperature of from about 20 C. to about 100 C.

'3. The cuprous complex produced by the reaction of cuprous nitrate with Z-methylcyclohexanone oxime at a temperature of from about 20 C. to'about 100 C.

4. The cuprous complex produced by the reaction of cuprous sulfate with 2,6-dimethylcyclohexanone oxime at v a temperature of from about'ZO" C. to about100 C.

The amount of dye on fiber or the depth of color are approximately pro ortional to the K/ S value which is a measure of the light re ected from the dyed sample. The larger the K/S value, the deeper the shade; and a K/S value of 20' is approximately twice as deep as a K/S value ofll). The determination of the K/S values is set forth in an article by D. B. glilgii g0l0l in Business, Science and Industry, 1952, pp.

No references cited. 

1. THE CUPROUS COMPLEX PRODUCED BY THE REACTION OF A CUPROUS SALT OF AN INORGANIC MINERAL ACID WITH A CYCLOHEXANONE OXIME OF THE FORMULA: 